Major-auxiliary cooperative metal pairs in MOFs enable cascade oxidation of KA oil to ε-caprolactone
Direct oxidation of KA oil (the mixture of cyclohexanone and cyclohexanol) toward ε-caprolactone is in high demand yet hard to implement in need of juggling the activation of both methyne C-H bond of cyclohexanol and α-C-C bond of cyclohexanone. Here we demonstrate that in situ formed Cu<sup>1+δ</sup>-O<sup>δ-•</sup> active site, which originates from relay reaction at Ni(II) and Cu(I) pairs in a metal-organic framework (known as NiCu-MOF-74) with O<sub>2</sub> and benzaldehyde (PhCHO), efficiently oxidizes KA oil toward ɛ-caprolactone along with good stability. Mechanism investigation discloses that the auxiliary Ni(II) site first adsorbs O<sub>2</sub> for abstracting formyl hydrogen in PhCHO followed by transfer of PhCO· to react with another O<sub>2</sub> over the major Cu(I) site, leading to formation of Cu<sup>1+δ</sup>-O<sup>δ-•</sup> and PhCOOH. This major-auxiliary cooperative strategy will be particularly suitable for multivariate MOFs as next generation catalysts towards complex reactions.
Authors
- Wenxing Chen (ORCID: https://orcid.org/0000-0001-9669-4358)
- Pengfei An (ORCID: https://orcid.org/0000-0001-7231-4218)
- Lirong Zheng (ORCID: https://orcid.org/0000-0003-0888-6769)
- Guangxin Xue
- Željka Ban (ORCID: https://orcid.org/0000-0002-6723-5811)
- Caoyu Yang (ORCID: https://orcid.org/0000-0003-0687-4270)
- Wei Liu (ORCID: https://orcid.org/0000-0001-6145-0660)
- Zhiyong Tang (ORCID: https://orcid.org/0000-0003-0610-0064)
- Ting Tan
- Guodong Li (ORCID: https://orcid.org/0000-0001-5099-4873)
- Hanlin Liu (ORCID: https://orcid.org/0009-0004-9923-0523)
Institutions
- Beijing Institute of Technology (CN)
- Chinese Academy of Sciences (CN)
- Institute of High Energy Physics (CN)
- National Center for Nanoscience and Technology (CN)
- University of Chinese Academy of Sciences (CN)
Publication Details
- Journal
- Nature Communications
- Published
- 2024-11-07
- DOI
- https://doi.org/10.1038/s41467-024-54064-w
- Citations
- 8
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 1.27
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Youth Innovation Promotion Association of the Chinese Academy of Sciences
- National Key Research and Development Program of China
- Youth Innovation Promotion Association
- Beijing Synchrotron Radiation Facility